CN105330862A - Preparation method of high-performance modified polysulfone resin - Google Patents
Preparation method of high-performance modified polysulfone resin Download PDFInfo
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- CN105330862A CN105330862A CN201510861128.1A CN201510861128A CN105330862A CN 105330862 A CN105330862 A CN 105330862A CN 201510861128 A CN201510861128 A CN 201510861128A CN 105330862 A CN105330862 A CN 105330862A
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Abstract
The invention discloses a preparation method of high-performance modified polysulfone resin. Monomers such as bisphenol A, 4,4'-dichlorodiphenyl sulfone and chain extender are used for preparing polysulfone resin, and then modification is conducted on the polysulfone resin through fibers, wherein when modification is conducted, a mixture comprises the components of 50%-90% of the polysulfone resin, 10%-50% of the fibers and 0.1%-5% of auxiliaries. According to the prepared high-performance modified polysulfone resin, the heat resistance is good, mechanical properties such as the stretching strength, the tensile strength, the tensile strength and the impact toughness can all be greatly improved after modification, and other excellent properties are kept constant.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of high-performance modified polysulfone resin (PSU).
Background technology
Polysulfones is a kind of thermoplastic engineering plastic, because they have thermotolerance, hot water resistance, creep resistance, dimensional stability, shock-resistance, chemical proofing, the excellent over-all properties such as nontoxic, fire-retardant, thus for a long time electronics, electrical equipment, machinery, automobile, medical apparatus, food-processing and not the field such as stickness paint be widely used.But because polysulfones processing temperature generally can more than 300 DEG C, in the course of processing, the defect due to self structure often causes resin portion to be decomposed, mechanical properties decrease thereupon, reduce the qualification rate of product.Carry out the research direction that the research of enhancement type polysulfones is polysulfone material in recent years, as carried out graft modification to polyethersulfone, in order to change the dielectric of polysulfones, the performance such as hydrophobic, mechanical, preparation high strength, multifunction polysulfone resin, expand its application in functional material.
Owing to containing Si in the chainextender that this invention uses, C, Ti, its bond energy is higher, and various spatial arrangement composition structure and the characteristic of self, determining its modified polysulfone material is a kind of Heat stability is good, mechanical property is high, high-low temperature resistant alternation performance, the material of low-dielectric energy and hydrophobic performance excellence, chainextender is while growth polymers molecular chain, the tensile strength of polymkeric substance and impelling strength are also improved greatly, thus the polysulfones of preparation is held concurrently resiniferous Hardness and toughness, possesses again the intensity of metal, open with mould Dai Gang epoch, greatly expand its practical application area.
At present, the most frequently used method carries out auxiliary agent blending and modifying, Chinese patent literature CN102532899A discloses and a kind ofly in polyethersulfone, adds titanium dioxide and glass fibre utilizes the physical method of mechanical blending to improve its comprehensive mechanical performance such as adhesiveproperties, consistency, but titanium dioxide can produce certain impact to the light transmission of resin and the shock strength of resin obviously be declined.Chinese patent literature CN102532899A discloses main chain and contains organo silicone polyether sulphone resin of line style and cage modle and preparation method thereof, by introducing polyethersulfone hydrophobic performance and the specific inductivity of the raising of functional molecular structure on polyethersulfone main chain, but the polyethersulfone color and luster that this method is synthesized is comparatively dark and transmittance is not high, is mainly limited to coating and field of microelectronic devices.Chinese patent literature CN102504271A discloses a kind of preparation method of hyperbranched polyester modified organic silicon resin, the advantages of superbrnaching end-hydroxy polyester and silicone resin is got up by the method, significantly improve the mechanical property of silicone resin, chemical resistance and water resistance, but snappiness is poor, can ftracture under high/low temperature alternation condition, limit its application.Select suitable chainextender, the ratio controlling itself and reaction monomers in the reasonable scope, is the key developing high strength, multi-functional polysulfone resin.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, the preparation method of high-performance modified polysulfone resin (PSU).
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for high-performance modified polysulfone resin, comprises the following steps:
(1) preparation of polysulfone resin
In the reactor of protection of inert gas, start stirring after adding organic solvent and be warming up to 60 DEG C ~ 80 DEG C, add dihydroxyphenyl propane, 4 in turn, 4 '-dichloro diphenyl sulfone monomer, after monomer all dissolves, then adds salt forming agent, the consumption of salt forming agent is 1.05 ~ 1.2 times of dihydroxyphenyl propane molar weight, add a point aqua subsequently, continue stirring and be warming up to 170 DEG C ~ 190 DEG C, salt-forming reaction 1 ~ 2 hour; All point aquas are steamed after salt-forming reaction completes, be warming up to 200 DEG C ~ 240 DEG C again, start to stir with the stirring velocity of 50 ~ 70 turns/min, constant temperature strengthens stirring velocity to 70 ~ 90 turn/min after 1 ~ 2 hour, continue constant temperature 4 ~ 5 hours, then add chainextender, the molar weight of chainextender is 0.1% ~ 10% of dihydroxyphenyl propane molar weight, continue reaction 40 minutes, to setting viscosity, obtain polymerization mucus; Cool, pulverize, wash, be drying to obtain polyethersulfone resin;
Described dihydroxyphenyl propane molar weight comparatively 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%, or, 4, the molar weight excessive compared with dihydroxyphenyl propane 0.1% ~ 2% of 4 '-dichloro diphenyl sulfone;
Described chainextender is the mixture of one or more in dichloro substituent, trichlorine substituent, tetrachloro substituent, and general structure is as follows:
Wherein, M is the one in C, Si, Ti; R
1, R
2, R
3for the one in chlorine, alkyl, alkoxyl group, cycloalkyl, phenyl, chloro alkyl; R
1, R
2, R
3middle amount of chlorine atom is 1 ~ 3; Atomic number of alkyl carbon is 1 ~ 18; Alkoxyl group carbonatoms is 1 ~ 20; Cycloalkyl carbon atoms number is 5 ~ 20; Phenyl carbons atomicity is 6 ~ 18; Chloro atomic number of alkyl carbon is 1 ~ 17;
(2) preparation of high-performance modified polysulfone resin
By gained polysulfone resin in convection oven 120 DEG C ~ 150 DEG C dry more than 8 hours, by fiber and auxiliary agent for subsequent use after about 60 DEG C dry pre-treatment; Dried polysulfone resin, fiber and auxiliary agent are mixed, then carries out melt extruding granulation with twin screw extruder, then pellet is dried more than 8h at 100 DEG C ~ 170 DEG C, by pellet injection moulding, obtain finished product.
Preferably, in step (2), each mixture ratio example is: polysulfone resin: 50 ~ 90%; Fiber: 10% ~ 50%; Auxiliary agent 0.1% ~ 5%.Further preferably, fiber: 20 ~ 30%.
Preferably, described organic solvent is selected from one or more in N-Methyl pyrrolidone, tetramethylene sulfone, sulfobenzide, methyl-sulphoxide, DMF, N,N-dimethylacetamide, trichloromethane, ethylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
Preferably, described point of aqua is selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene or one or more partially in diethylbenzene.
Preferably, the boiling point of described point of aqua is higher than 160 DEG C lower than 200 DEG C, and density is less than water.It is such as the mixture of one or more in sym-trimethylbenzene, hemimellitol, a trimethylbenzene, diethylbenzene, partially diethylbenzene.
Preferably, described salt forming agent is selected from potassium hydroxide, salt of wormwood, sodium hydroxide, one or more in sodium carbonate.Preferred sodium carbonate further.
Preferably, described fiber is one or more in glass fibre, carbon fiber, aramid fiber, Kevlar fiber, basalt fibre, propionitrile fiber, boron fibre, whisker.
Preferably, described auxiliary agent is one or more in oxidation inhibitor, thermo-stabilizer, toughner, fire retardant, antifogging agent, static inhibitor, impact modifying agent, expanding material, tinting material.
Preferably, be 25% ~ 30% at the solid content of salt-forming reaction stage system.
Preferably, be 35% ~ 45% at the solid content of polymerization stage system.
The present invention compared with prior art, has following beneficial effect:
1) the present invention is by controlling two chlorine and biphenol monomer ratio, first, synthesize hydroxy-end capped polysulfone oligomer, and further by accessing the low molecule organic matter of carbon containing, silicon, titanium on hydroxy-end capped polysulfone oligomer containing dichloro substituent, trichlorine substituent or tetrachloro substituent, prepare the high strength polysulfone resin that main chain contains carbon, silicon, titanium;
2) the present invention carries out modification by fiber and auxiliary agent to high strength polysulfone resin (PSU), the modified high performance polysulfone resin obtained, improves rigidity, flexural strength, tensile strength, anti-tensile, thermotolerance, dimensional stability and reduces molding shrinkage;
3) the present invention to main chain contain carbon, silicon, titanium polysulfone resin (PSU) carry out modification, technique is simple, excellent effect.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
Embodiment 1
In the reactor of protection of inert gas, start stirring after adding sulfolane solvent and be warming up to 60 DEG C ~ 80 DEG C, add dihydroxyphenyl propane, 4 in turn, 4 '-dichloro diphenyl sulfone monomer, after monomer all dissolves, then adds salt forming agent, the consumption of salt forming agent is 1.05 ~ 1.2 times of dihydroxyphenyl propane molar weight, add a point aqua subsequently, continue stirring and be warming up to 170 DEG C ~ 190 DEG C, salt-forming reaction 1 ~ 2 hour; All point aquas are steamed after salt-forming reaction completes, be warming up to 200 DEG C ~ 240 DEG C again, start to stir with the stirring velocity of 50 ~ 70 turns/min, constant temperature strengthens stirring velocity to 70 ~ 90 turn/min after 1 ~ 2 hour, continue constant temperature 4 ~ 5 hours, then add chainextender, the molar weight of chainextender is 0.1% ~ 10% of dihydroxyphenyl propane molar weight, continue reaction 40 minutes, to setting viscosity, obtain polymerization mucus; Cool, pulverize, wash, be drying to obtain polyethersulfone resin;
Described dihydroxyphenyl propane molar weight comparatively 4,4 '-dichloro diphenyl sulfone excessive 2%.
Described chain extender structures general formula is as follows:
Wherein, M is C; R
1, R
2, R
3for chlorine.
By gained polysulfone resin in convection oven 130 DEG C dry 12 hours, glass fibre and auxiliary agent are dried 8h at 60 DEG C.Dried raw material is pressed polysulfone resin 69%, glass fibre 30%, oxidation inhibitor: 0.1%; Softening agent: 0.1%, the ratio of toughner 0.1%, thermo-stabilizer 0.7% mixes, then carry out melt extruding granulation according to expressing technique with twin screw extruder, again pellet 100 DEG C is dried 12 hours, select suitable to extrude, pellet injection moulding obtains standard test specimen by Shooting Technique, finally carry out performance test.
Embodiment 2
With embodiment 1, except substituting except glass fibre with carbon fiber, other conditions are identical, and test result sees the following form.
Embodiment 3
With embodiment 1, except substituting except glass fibre with aramid fiber, other conditions are identical, and test result sees the following form.
Embodiment 4
With embodiment 1, except substituting except glass fibre with Kevlar fiber, other conditions are identical, and test result sees the following form.
Comparative example 1
With embodiment 1, except not adding any filler, other conditions are identical, and test result sees the following form.
Claims (10)
1. a preparation method for high-performance modified polysulfone resin, is characterized in that, comprises the following steps:
(1) preparation of polysulfone resin
In the reactor of protection of inert gas, start stirring after adding organic solvent and be warming up to 60 DEG C ~ 80 DEG C, add dihydroxyphenyl propane, 4 in turn, 4 '-dichloro diphenyl sulfone monomer, after monomer all dissolves, then adds salt forming agent, the consumption of salt forming agent is 1.05 ~ 1.2 times of dihydroxyphenyl propane molar weight, add a point aqua subsequently, continue stirring and be warming up to 170 DEG C ~ 190 DEG C, salt-forming reaction 1 ~ 2 hour; All point aquas are steamed after salt-forming reaction completes, be warming up to 200 DEG C ~ 240 DEG C again, start to stir with the stirring velocity of 50 ~ 70 turns/min, constant temperature strengthens stirring velocity to 70 ~ 90 turn/min after 1 ~ 2 hour, continue constant temperature 4 ~ 5 hours, then add chainextender, the molar weight of chainextender is 0.1% ~ 10% of dihydroxyphenyl propane molar weight, continue reaction 40 minutes, to setting viscosity, obtain polymerization mucus; Cool, pulverize, wash, be drying to obtain polysulfone resin;
Described dihydroxyphenyl propane molar weight comparatively 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%, or, 4, the molar weight excessive compared with dihydroxyphenyl propane 0.1% ~ 2% of 4 '-dichloro diphenyl sulfone;
Described chainextender is the mixture of one or more in dichloro substituent, trichlorine substituent, tetrachloro substituent, and general structure is as follows:
Wherein, M is the one in C, Si, Ti; R
1, R
2, R
3for the one in chlorine, alkyl, alkoxyl group, cycloalkyl, phenyl, chloro alkyl; R
1, R
2, R
3middle amount of chlorine atom is 1 ~ 3; Atomic number of alkyl carbon is 1 ~ 18; Alkoxyl group carbonatoms is 1 ~ 20; Cycloalkyl carbon atoms number is 5 ~ 20; Phenyl carbons atomicity is 6 ~ 18; Chloro atomic number of alkyl carbon is 1 ~ 17;
(2) preparation of high-performance modified polysulfone resin
By gained polysulfone resin in convection oven 120 DEG C ~ 150 DEG C dry more than 8 hours, by fiber and auxiliary agent for subsequent use after about 60 DEG C dry pre-treatment; Dried polysulfone resin, fiber and auxiliary agent are mixed, then carries out melt extruding granulation with twin screw extruder, then pellet is dried more than 8h at 100 DEG C ~ 170 DEG C, by pellet injection moulding, obtain finished product.
2. method according to claim 1, is characterized in that, in step (2), each mixture ratio example is: polysulfone resin: 50 ~ 90%; Fiber: 10% ~ 50%; Auxiliary agent 0.1% ~ 5%.
3. method according to claim 1, it is characterized in that, described organic solvent is selected from N-Methyl pyrrolidone, tetramethylene sulfone, sulfobenzide, methyl-sulphoxide, N, dinethylformamide, N, one or more in N-N,N-DIMETHYLACETAMIDE, trichloromethane, ethylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
4. method according to claim 1, is characterized in that, described point of aqua is selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene or one or more partially in diethylbenzene.
5. method according to claim 1, is characterized in that, the boiling point of described point of aqua is higher than 160 DEG C lower than 200 DEG C, and density is less than water.
6. method according to claim 1, is characterized in that, described salt forming agent is selected from potassium hydroxide, salt of wormwood, sodium hydroxide, one or more in sodium carbonate.
7. method according to claim 1, is characterized in that, described fiber is one or more in glass fibre, carbon fiber, aramid fiber, Kevlar fiber, basalt fibre, propionitrile fiber, boron fibre, whisker.
8. method according to claim 1, is characterized in that, described auxiliary agent is one or more in oxidation inhibitor, thermo-stabilizer, toughner, fire retardant, antifogging agent, static inhibitor, impact modifying agent, expanding material, tinting material.
9. method according to claim 1, is characterized in that, is 25% ~ 30% at the solid content of salt-forming reaction stage system.
10. method according to claim 1, is characterized in that, is 35% ~ 45% at the solid content of polymerization stage system.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286345A (en) * | 2017-07-27 | 2017-10-24 | 上海帕斯砜材料科技有限公司 | High-purity polysulfones, polyether sulfone, polyaryl sulphone industrialized preparing process |
| CN110272545A (en) * | 2019-06-12 | 2019-09-24 | 扬州清研高分子新材料有限公司 | A kind of processing method shortening the polysulfones production cycle |
| CN110358088A (en) * | 2019-06-06 | 2019-10-22 | 南京清研高分子新材料有限公司 | A method of preparing polysulfones |
| CN112194896A (en) * | 2020-09-08 | 2021-01-08 | 威海金泓管材有限公司 | Polysulfone resin for preparing water collecting and distributing device and preparation method thereof |
| CN112251179A (en) * | 2020-10-27 | 2021-01-22 | 烟台德邦科技有限公司 | Preparation method of polysulfone resin modified epoxy structural adhesive |
| CN115785672A (en) * | 2022-12-07 | 2023-03-14 | 广东优巨先进新材料股份有限公司 | Polyphenylene sulfone composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
| CN103382305A (en) * | 2012-05-04 | 2013-11-06 | 金发科技股份有限公司 | Alloy of polysulfone resin and semi-aromatic nylon and preparation method thereof |
| CN104530419A (en) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | Industrial synthesis method of high-thermal-stability terminated polysulfone resin |
| CN104530431A (en) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | Industrial synthetic method of low-color high-transmittance polysulfone resin |
-
2015
- 2015-11-30 CN CN201510861128.1A patent/CN105330862B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
| CN103382305A (en) * | 2012-05-04 | 2013-11-06 | 金发科技股份有限公司 | Alloy of polysulfone resin and semi-aromatic nylon and preparation method thereof |
| CN104530419A (en) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | Industrial synthesis method of high-thermal-stability terminated polysulfone resin |
| CN104530431A (en) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | Industrial synthetic method of low-color high-transmittance polysulfone resin |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286345A (en) * | 2017-07-27 | 2017-10-24 | 上海帕斯砜材料科技有限公司 | High-purity polysulfones, polyether sulfone, polyaryl sulphone industrialized preparing process |
| CN107286345B (en) * | 2017-07-27 | 2023-08-18 | 上海帕斯砜材料科技有限公司 | Industrial production method of high-purity polysulfone, polyether sulfone and polyarylsulfone resin |
| CN110358088A (en) * | 2019-06-06 | 2019-10-22 | 南京清研高分子新材料有限公司 | A method of preparing polysulfones |
| CN110358088B (en) * | 2019-06-06 | 2020-04-07 | 南京清研高分子新材料有限公司 | Method for preparing polysulfone |
| CN110272545A (en) * | 2019-06-12 | 2019-09-24 | 扬州清研高分子新材料有限公司 | A kind of processing method shortening the polysulfones production cycle |
| CN110272545B (en) * | 2019-06-12 | 2020-08-04 | 扬州清研高分子新材料有限公司 | Processing method for shortening polysulfone production period |
| CN112194896A (en) * | 2020-09-08 | 2021-01-08 | 威海金泓管材有限公司 | Polysulfone resin for preparing water collecting and distributing device and preparation method thereof |
| CN112194896B (en) * | 2020-09-08 | 2023-03-28 | 威海金泓管材有限公司 | Polysulfone resin for preparing water collecting and distributing device and preparation method thereof |
| CN112251179A (en) * | 2020-10-27 | 2021-01-22 | 烟台德邦科技有限公司 | Preparation method of polysulfone resin modified epoxy structural adhesive |
| CN115785672A (en) * | 2022-12-07 | 2023-03-14 | 广东优巨先进新材料股份有限公司 | Polyphenylene sulfone composite material and preparation method and application thereof |
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